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Patented Dec. 2, 1930 UNITED FSTATES" P T NT ARTHUR Lum'rnmermus AND FILIP KAcnn, or 1M1;ANLNHEIM, GI LBLlVfAlbTS f, ASSIGNWCHRS no i GENERAL ANILINE wonxs, me, or nnw yonx N; 355a CORPORATION OFDEIZA-V WARE i I ANTHRAQUINONE-THIOXANTHQNE,#A'I DYESTITFTS l No Drawing. Application men/larc 6,1928, Serial Na. M nam Germany March 10,192"7 The present invention relates to improve fments in vat dyestuifs series.

We have found that particularly valuable vat dyestuifs ofthe saidseries are produced by causing ring formation to take place,by

treatment with dehydratingag'ents, in those ethers of mercapto-anthraquinone-carboXylic acids, which are obtainable by the conden'sa: tion, for example, of 2 molecular proportions of a l-chloranthraquinone-2-carboxylic acid with 1 molecular proportion of a 2.6- or (which may 2.7-dimercaptoanthraquinone be obtained, for example, by boiling a 2.6- or 2.7-dichloranthraquinone respectively with alcoholic sodium sulfide or polysulfide), or

by the condensation of 2 molecular proportions of a l-mercaptoanthraquinone-2-carboxylic acid with 1 molecular proportion ofa 2.6- or 2.7-tetrazoanthraquinone-sulfate, or by the condensation of 2 molecular propore.

tions of a 1 diazoanthraquinone 2-carboxylic acid with 1 molecular proportionof a 2.6: or 2.7 dimercaptoanthraquinone andwhich arethereforebis- (2' carboxy-anthraquinonyh 1'?) -diamercapto-2.6-, or 2.7-anthraquinones of the general formulae: V

and

For the performance of the present process also'thesalts of the said carboxyli'c acidsin ay be employed, whichytherefore, are regarded as equivalents for the said purpose. These dyestuffs, in which 3 anthraquinone radicles are connected with each other in the molecule and which correspond probably to the for mulae and are distinguished from theanthraquinonethioxanthones hitherto known, by possessing particularly high tinctorial power, and by giving strong yellow shades also from the warm hydrosulfite vat; they are therefore 1 tratehow the said invention maybe carried out in practice, but the invention is not limited thereto. .The parts are by weight.

drosulfite Vat is greyish-blue.

Ewample 1 A sulfuric acid solution of 1.2anthraquinoneisoxazol is prepared from partsof 1- nitro-2-methylanthraquinone, for example by treating the latter with fuming sulfuric acid and running the nnxture lnto cooled, dilute (1, nitrosylsulfuric acid and diluting with Water while cooling. A solution of 13 parts of 2.7-dimercaptoanthraquinone in 400 parts of water and parts of caustic soda. solution'of 30 Beaum is stirred into this solution, which is still strongly acid, at room temperature. Nitrogen is disengaged, and a yellow precipitate of the bis- (2'-carboxyanthraquinonyl-1-) -dimercapto-2.7 -anthraquinone is produced. The mixture is raised to boiling heat and the precipitate filtered off by suction, washed with water and dried.

10 parts of the acid obtained in the above or any other suitable manner, and which may be purified, if necessary, for instance by way of its sodium salt, are heated to centigrade with parts of sulfuric acid of 66 Beaum for an hour. The yellow-red sulfuric acid solution is stirred into water, the precipitated dyestuff being filtered by suction and washed until neutral. It may be further purified by treatment with sodium hypochlorite solution. It can be obtained in a specially pure state by fractional precipitation from its solution in sulfuric acid. The dyestuif'dissolves to a yellow-red solution in sulfuric acid. The hy- Emample 2 10 parts ofbis- (2-carboxy-anthraquinonyll-) dimercapto-Z'T-anthraquinone :are boiled with 200 parts of benzotrichlorid for from 6 to 7 hours. Formation of the acid chl'orid takes place first, which is followed by that of the dyestufi". After cooling, the product is washed with benzotrichlorid and alcohol and then dried. The yellow powder may be used for dyeing as such or, if desired, may be purified before use.

If, in the foregoing examples, the 2.7-dimercaptoanthraquinone be replaced by the 2.6-dimercaptoanthraquinone a Very similar dyestuif will be obtained.

The ring formation may also be effected by means of other suitable agents, such as other acid halides or acid anhydrides.

What we claim is:

1. As new articles of manufacture the yellow dyestuffs, which correspond probably to the formulae and dye cotton strong yellow shades and are obtainable by treating with a dehydrating agent a bis-(2-carboxy-anthroqninonyl-1-) d-iinercapto-Banthraquirione in which the twosubstituted fipbsitions are not vici-nal.

2. As a new article of manufacture the yellow dyestuff which corresponds probably to the formula ARTHUR LUTTRINGHAUS. FILIP KACER.

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